CN105655592B - A kind of negative electrode of lithium ion battery and preparation method thereof based on silicon - Google Patents
A kind of negative electrode of lithium ion battery and preparation method thereof based on silicon Download PDFInfo
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- CN105655592B CN105655592B CN201610142109.8A CN201610142109A CN105655592B CN 105655592 B CN105655592 B CN 105655592B CN 201610142109 A CN201610142109 A CN 201610142109A CN 105655592 B CN105655592 B CN 105655592B
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 68
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 29
- 239000010439 graphite Substances 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 17
- 239000002562 thickening agent Substances 0.000 claims abstract description 14
- 239000004743 Polypropylene Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 13
- 229920001155 polypropylene Polymers 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004793 Polystyrene Substances 0.000 claims abstract description 11
- 239000011889 copper foil Substances 0.000 claims abstract description 11
- 239000011267 electrode slurry Substances 0.000 claims abstract description 11
- 229920002223 polystyrene Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 16
- 239000006256 anode slurry Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000004816 latex Substances 0.000 claims description 10
- 229920000126 latex Polymers 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910021389 graphene Inorganic materials 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention is a kind of negative electrode of lithium ion battery and preparation method thereof based on silicon, it is coated on copper foil by negative electrode slurry and is prepared, the formula of negative electrode slurry are as follows: graphite 15.0-18.0 parts by weight, nano silica fume 1.0-2.0 parts by weight, conductive agent 0.3-2.5 parts by weight, binder 1.0-8.0 parts by weight, thickener 1.0-1.5 parts by weight, decentralized medium 70.0-80.0 parts by weight；Polystyrene-polypropylene acid butyl ester-polystyrene block polymeric binder is used in the present invention, there is high cohesive force to silicon, and it can provide high resiliency, volume change of the offset silicon in charge and discharge, improve the negative electrode of lithium ion battery performance based on graphene, obtained high-energy density type cathode has 514mAh/g energy density in 0.1C charge and discharge, and power-type cathode has 349mAh/g energy density in 2C charge and discharge.Raw material of the present invention is easy to get, simple process, environmental protection.
Description
Technical field
The present invention relates to a kind of lithium ion battery based on silicon more particularly to a kind of negative electrode of lithium ion battery based on silicon and
Preparation method.
Background technique
Lithium ion battery begins one's study and develops in last century early eighties, is initially mainly used for portable device, with
Its market continuous enlargement, importance effect has also been played in all types of electric cars and energy-storage system.With it is traditional secondary
Battery is compared, lithium ion battery energy density per unit volume with higher and specific energy, and battery can be made to become smaller, lighter,
And opposite energy conservation and environmental protection, apparent advantage and wide application prospect make the research hotspot being widely noticed.Currently
The active material that commercialized negative electrode of lithium ion battery uses is graphite material, and theoretical capacity is about 370mAh/g, although stone
Ink material has many advantages, such as, but 1/10th of theoretical specific capacity not as good as lithium an- ode theoretical capacity.It urgently develops at present
New high capacity, the cathode in long circulation life service life substitute graphite material.
The embedding lithium theoretical specific capacity of silicon is up to 4200mAh/g, thus becomes one of the negative electrode active material of most attraction.
However, there are serious volume changes, up to 400% in charge and discharge for silicon, causes cycle performance of battery very poor, hinder its
Commercial applications.Thus how to eliminate the mechanical stress that silicon generates during removal lithium embedded by volume change becomes heavy to closing
It wants.In addition, silicon itself is semiconductor, conductivity is poor, needs to be added conductive agent to improve the electronic conduction of electrode.
Traditional cathode is polyvinylidene fluoride (PVDF) and butadiene-styrene rubber (SBR) with binder.PVDF is for a long time
Main adhesive to be used in lithium battery positive and negative anodes, it has good electrochemistry, chemistry, thermal stability, there is higher machinery
Intensity meets the basic demand of electrode adhesive and is widely used.But the caking property of PVDF belongs in many adhesives
It is easy to cause electrode active material, especially silicon materials to become in impulse electricity volume in poor, poor caking property and elasticity
It is detached from during change with adhesive and graphite, causes battery capacity decaying too fast.Recently, high viscoplasticity adhesive butadiene-styrene rubber water
Base adhesive starts gradually to substitute PVDF.Since the presence of polybutadiene phase is a kind of adhesive that viscoplasticity is excellent in SBR, though
So SBR shows excellent performance in conventional lithium ion battery, but performance is appointed in the cathode there are nano silicon material
So shortcoming is a greater impact to the cohesive force of silicon materials after being primarily due to SBR swelling electrolyte, and SBR is as binder
It is unable to satisfy and eliminates the requirement that silicon generates stress in removal lithium embedded because of volume change.
Summary of the invention
It is low not the purpose of the invention is to overcome the prior art that specific capacity when graphite does negative electrode active material is used only
Foot, provides a kind of negative electrode of lithium ion battery and preparation method thereof based on silicon.
The purpose of the present invention is what is realized by following technical solution: a kind of lithium ion battery based on silicon is negative
Pole, the negative electrode of lithium ion battery are to be coated in negative electrode slurry on copper foil to be prepared, and thickness is between 50-300 microns, institute
The formula for the negative electrode slurry stated are as follows: graphite 15.0-18.0 parts by weight, nano silica fume 1.0-2.0 parts by weight, conductive agent 0.3-2.5
Parts by weight, binder 1.0-8.0 parts by weight, thickener 1.0-1.5 parts by weight, decentralized medium 70.0-80.0 parts by weight；It is described viscous
Tying agent is polystyrene-polypropylene acid butyl ester-polystyrene block type copolymer water-based latex.
Further, the partial size of the graphite is 300-500 mesh, fixed carbon content >=99.0%；The nano-silicon
The average diameter of powder is at 50-100 nanometers.
Further, the conductive agent can select Super P, Super S, acetylene black, carbon nanotube or carbon fiber.
Further, the thickener is sodium carboxymethylcellulose.
Further, the decentralized medium is deionized water.
The preparation method of the above-mentioned negative electrode of lithium ion battery based on silicon, includes the following steps:
(1) thickener of 1.0-1.5 parts by weight, the conductive agent of 0.3-2.5 parts by weight, 15.0- are added in ball mill
The graphite of 18.0 parts by weight and the nano silica fume of 1.0-2.0 parts by weight, ball milling 120-180 minutes；
(2) step 1 resulting material is transferred to vacuum stirring cylinder, the bonding of 1.0-8.0 parts by weight is added in blender
The decentralized medium of agent and 46.67-53.33 parts by weight stirs at low speed 5-15 minutes, scraper after stirring, then high-speed stirred 45-
60 minutes；
(3) decentralized medium of 23.33-26.67 parts by weight is added in the material obtained by step 2, stirs at low speed 5-
15 minutes, scraper after stirring high-speed stirred 45-60 minutes, obtained the lithium ion battery anode slurry；
(4) negative electrode slurry for obtaining step 3 is coated on copper foil, and coating thickness obtains base between 50-300 microns
In the negative electrode of lithium ion battery of silicon.
Further, the step 2 and 3 carries out under 0.3-0.5bar vacuum degree condition.
Further, the rotational speed of ball-mill of the step 1 is 150-300r/min.
Further, in the step 2 and 3, stirring at low speed speed is 30-50r/min, and high-speed stirred speed is 150-
200r/min。
The invention has the advantages that the present invention is using polystyrene-polypropylene acid butyl ester-polystyrene block type copolymerization
The negative electrode of lithium ion battery based on silicon is prepared in object binder, has the characteristics that following:
1, silicon is doped into negative electrode of lithium ion battery, opposite conventional lithium ion battery graphite cathode specific energy, power-performance
It is greatly improved.
2, cathode preparation uses water-based emulsion type binder, avoids using organic solvent, process environmental protection.
3, the negative electrode binder in the present invention uses block type polymers, realizes microcosmic two-phase by mutually separating.Wherein, benzene
The pi bond active force of ethylene phase and silicon is strong, and non-swelling electrolyte in the battery, it is ensured that the high cohesive force of silicon；Polypropylene
Acid butyl ester block is swollen electrolyte, provides lithium ion transport channel, can not influence cohesive force by improving electrolyte dosage
Under the premise of greatly improve lithium ion transport rate；Meanwhile butyl polyacrylate elasticity is excellent, the offset silicon in charge and discharge process
Volume deformation.Two phase separations are different, are independent of each other, but avoid the separation of generation macroface further through the connection of chemical bond and lead to silicon
With binder it is poly- simultaneously.The negative electrode of lithium ion battery cycle performance based on silicon is improved, obtained high-energy type cathode can reach
The capacity of 514mAh/g；High power type negative electrode material can still have the capacity of 349mAh/g in 1C.
4, in the present invention raw material that uses be easy to get, process equipment requirement it is low.
Detailed description of the invention
Fig. 1 is the silicon lithium ion battery cathode energy density test chart that embodiment 1 obtains；
Fig. 2 is the silicon lithium ion battery cathode energy density test chart that embodiment 2 obtains；
Fig. 3 is the silicon lithium ion battery cathode energy density test chart that embodiment 3 obtains.
Specific embodiment
The present invention provides a kind of negative electrode of lithium ion battery based on silicon, and the negative electrode of lithium ion battery is to apply negative electrode slurry
It overlays on copper foil and is prepared, thickness is between 50-300 microns, the formula of the negative electrode slurry are as follows: graphite 15.0-18.0
Parts by weight, nano silica fume 1.0-2.0 parts by weight, conductive agent 0.3-2.5 parts by weight, binder 1.0-8.0 parts by weight, thickener
1.0-1.5 parts by weight, decentralized medium 70.0-80.0 parts by weight；The binder is polystyrene-polypropylene acid butyl ester-polyphenyl
Ethylene block type copolymer water-based latex.
The partial size of the graphite is 300-500 mesh, fixed carbon content >=99.0%.
The average diameter of the nano silica fume is at 50-100 nanometers.
The polystyrene-polypropylene acid butyl ester-polystyrene block type copolymer water-based latex, block copolymer
Amount is (15-50) K- (40-150) K- (15-50) K, and the latex solid content is 15-35%.The polystyrene-polypropylene acid
Butyl ester-polystyrene block type copolymer water-based latex preparation method is detailed in the hair of Patent No. " ZL200910099918.5 "
Bright patent document.
The thickener is sodium carboxymethylcellulose.
The decentralized medium is deionized water.
The conductive agent can select Super P, Super S, acetylene black, carbon nanotube or carbon fiber.
The present invention is based on the negative electrode of lithium ion battery of silicon to be prepared by the following method to obtain:
(1) thickener of 1.0-1.5 parts by weight, the conductive agent of 0.3-2.5 parts by weight, 15.0- are added in ball mill
The graphite of 18.0 parts by weight and the nano silica fume of 1.0-2.0 parts by weight, ball milling 120-180 minutes；
(2) step 1 resulting material is transferred to vacuum stirring cylinder, the bonding of 1.0-8.0 parts by weight is added in blender
The decentralized medium of agent and 46.67-53.33 parts by weight stirs at low speed 5-15 minutes, scraper after stirring, then high-speed stirred 45-
60 minutes；
(3) decentralized medium of 23.33-26.67 parts by weight is added in the material obtained by step 2, stirs at low speed 5-
15 minutes, scraper after stirring high-speed stirred 45-60 minutes, obtained the lithium ion battery anode slurry；
(4) negative electrode slurry for obtaining step 3 is coated on copper foil, and coating thickness obtains base between 50-300 microns
In the negative electrode of lithium ion battery of silicon.
The step 2 and 3 carries out under 0.3-0.5bar vacuum degree condition.
The rotational speed of ball-mill of the step 1 is 150-300r/min.
In the step 2 and 3, stirring at low speed speed is 30-50r/min, and high-speed stirred speed is 150-200r/min.
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with the drawings and specific embodiments,
The present invention is described in more detail.
Embodiment 1:
Lithium ion battery anode slurry is coated on copper foil and prepares negative electrode of lithium ion battery, thickness is at 50 microns.Slurry
In each parts by weight of raw materials than formula be are as follows: 15.0 parts by weight of graphite, 2.0 parts by weight of nano silica fume, 2.5 parts by weight of conductive agent are glued
Tie 5.0 parts by weight of agent, 1.0 parts by weight of sodium carboxymethylcellulose, 70.0 parts by weight of deionized water.The partial size of the graphite is
300 mesh, fixed carbon content >=99.8%；The average diameter of nano silica fume is about 50 nanometers；The conductive agent is Super P；Institute
Stating binder is polystyrene-polypropylene acid butyl ester-polystyrene block type copolymer emulsion, and block copolymer amount is
15k-100 k-15k, latex solid content are 35%.
The lithium ion battery anode slurry is prepared: 1. by formula of size in ball mill by following processing technology
In each raw material weight/power ratio be added whole thickeners, whole conductive agents, whole graphite and whole nano silica fumes, ball milling 180 minutes；②
It incites somebody to action 1. resulting material be transferred in vacuum stirring cylinder, is added and is formulated weight/power ratio by whole binders of formula weight/power ratio and 2/3
Decentralized medium stirs at low speed 15 minutes, scraper after stirring, and high-speed stirred 60 minutes；3. in process 2. obtained material
The middle decentralized medium that residue 1/3 is added and is formulated weight/power ratio, stirs at low speed 5 minutes, scraper after stirring, high-speed stirred 45 is divided
Clock obtains the lithium ion battery anode slurry.1. process carries out under normal pressure, 2., 3. process is in 0.5bar vacuum degree item
It is carried out under part.Rotational speed of ball-mill is 300r/min；Stirring at low speed speed is 50r/min；High-speed stirred speed is 200r/min.
The formula prepares high-energy density type negative electrode of lithium ion battery, as shown in Figure 1, being used as using metal lithium sheet to electrode
2032 type button half-cells are prepared with gained negative electrode of lithium ion battery, gained cathode energy is close in the test of 0.1C charge and discharge cycles
Degree is about 480mAh/g, is much higher than conventional graphite energy density on cathode, energy density would be about 349mAh/g in 1C charge and discharge.
Embodiment 2:
Lithium ion battery anode slurry is coated on copper foil and prepares negative electrode of lithium ion battery, thickness is at 300 microns.Slurry
In each parts by weight of raw materials than formula are as follows: 18.0 parts by weight of graphite, 1.0 parts by weight of nano silica fume, 0.3 parts by weight of conductive agent, bonding
8.0 parts by weight of agent, 1.5 parts by weight of sodium carboxymethylcellulose, 80.0 parts by weight of deionized water.The partial size of the graphite is 400
Mesh, fixed carbon content >=99.5%；The average diameter of nano silica fume is at 80 nanometers；The conductive agent is Super S；The bonding
Agent is polystyrene-polypropylene acid butyl ester-polystyrene block type copolymer emulsion, and block copolymer amount is 50k-150
K-50k, latex solid content are 15%.
The lithium ion battery anode slurry is prepared: 1. by formula of size in ball mill by following processing technology
In each raw material weight/power ratio be added whole thickeners, whole conductive agents, whole graphite and whole nano silica fumes, ball milling 120 minutes；②
It incites somebody to action 1. resulting material be transferred in vacuum stirring cylinder, is added and is formulated weight/power ratio by whole binders of formula weight/power ratio and 2/3
Decentralized medium stirs at low speed 5 minutes, scraper after stirring, and high-speed stirred 45 minutes；3. in process 2. obtained material
The decentralized medium that residue 1/3 is formulated weight/power ratio is added, stirs at low speed 15 minutes, scraper after stirring, high-speed stirred 60 minutes,
Obtain the lithium ion battery anode slurry.1. process carries out under normal pressure, 2., 3. process under 0.3bar vacuum degree condition
It carries out.Rotational speed of ball-mill is 150r/min；Stirring at low speed speed is 30r/min；High-speed stirred speed is 150r/min.
The formula prepares power-type lithium ion battery cathode, as shown in Fig. 2, being used as using metal lithium sheet to electrode and gained
Negative electrode of lithium ion battery prepares 2032 type button half-cells, and gained energy density on cathode is about in the test of 0.1C charge and discharge cycles
443mAh/g is higher than conventional graphite energy density on cathode, and in 1C charge and discharge, energy density is about 303mAh/g, better than traditional stone
Energy density of the black cathode in the current charging and discharging.
Embodiment 3:
Lithium ion battery anode slurry is coated on copper foil and prepares negative electrode of lithium ion battery, thickness is at 50 microns.Slurry
In each parts by weight of raw materials than formula are as follows: graphite: 15 parts by weight, 2 parts by weight of nano silica fume, 2.0 parts by weight of conductive agent, binder
1.0 parts by weight, 1.0 parts by weight of sodium carboxymethylcellulose, 80.0 parts by weight of deionized water.The partial size of the graphite is 500 mesh,
Fixed carbon content >=99.9%；The average diameter of nano silica fume is in 100 rans；The conductive agent is carbon nanotube；It is described
Binder is polystyrene-polypropylene acid butyl ester-polystyrene block type copolymer emulsion, and block copolymer amount is 15k-
40 k-15k, latex solid content are 30%.
The lithium ion battery anode slurry is prepared: 1. by formula of size in ball mill by following processing technology
In each raw material weight/power ratio be added whole thickeners, whole conductive agents, whole graphite and whole nano silica fumes, ball milling 180 minutes；②
It incites somebody to action 1. resulting material be transferred in vacuum stirring cylinder, is added and is formulated weight/power ratio by whole binders of formula weight/power ratio and 2/3
Decentralized medium stirs at low speed 10 minutes, scraper after stirring, and high-speed stirred 45 minutes；3. in process 2. obtained material
The middle decentralized medium that residue 1/3 is added and is formulated weight/power ratio, stirs at low speed 10 minutes, scraper after stirring, high-speed stirred 60 is divided
Clock obtains the lithium ion battery anode slurry.1. process carries out under normal pressure, 2., 3. process is in 0.4bar vacuum degree item
It is carried out under part.Rotational speed of ball-mill is 200r/min；Stirring at low speed speed is 25r/min；High-speed stirred speed is 180r/min.
The formula prepares power-type lithium ion battery cathode, as shown in figure 3, being used as using metal lithium sheet to electrode and gained
Negative electrode of lithium ion battery prepares 2032 type button half-cells, and gained energy density on cathode is about in the test of 0.1C charge and discharge cycles
514mAh/g is higher than conventional graphite energy density on cathode, and in 1C charge and discharge, energy density is about 328mAh/g, better than traditional stone
Energy density of the black cathode in the current charging and discharging.
Embodiment 4:
Lithium ion battery anode slurry is coated on copper foil and prepares negative electrode of lithium ion battery, thickness is at 100 microns.Slurry
In each parts by weight of raw materials than formula are as follows: graphite: 16 parts by weight, 1.5 parts by weight of nano silica fume, 0.5 parts by weight of conductive agent, binder
2.7 parts by weight, 1.3 parts by weight of sodium carboxymethylcellulose, 78.0 parts by weight of deionized water.The partial size of the graphite is 450 mesh,
Fixed carbon content >=99.9%；The average diameter of nano silica fume is in 100 rans；The conductive agent is acetylene black；It is described viscous
Knot agent is polystyrene-polypropylene acid butyl ester-polystyrene block type copolymer emulsion, and block copolymer amount is 30k-
100 k-30k, latex solid content are 25%.
The lithium ion battery anode slurry is prepared: 1. by formula of size in ball mill by following processing technology
In each raw material weight/power ratio be added whole thickeners, whole conductive agents, whole graphite and whole nano silica fumes, ball milling 150 minutes；②
It incites somebody to action 1. resulting material be transferred in vacuum stirring cylinder, is added and is formulated weight/power ratio by whole binders of formula weight/power ratio and 2/3
Decentralized medium stirs at low speed 13 minutes, scraper after stirring, and high-speed stirred 50 minutes；3. in process 2. obtained material
The middle decentralized medium that residue 1/3 is added and is formulated weight/power ratio, stirs at low speed 13 minutes, scraper after stirring, high-speed stirred 50 is divided
Clock obtains the lithium ion battery anode slurry.1. process carries out under normal pressure, 2., 3. process is in 0.5bar vacuum degree item
It is carried out under part.Rotational speed of ball-mill is 250r/min；Stirring at low speed speed is 40r/min；High-speed stirred speed is 160r/min.
The formula prepares power-type lithium ion battery cathode, is used as using metal lithium sheet to electrode and gained lithium ion battery
Cathode prepares 2032 type button half-cells, and in the test of 0.1C charge and discharge cycles and 1C charge and discharge, energy density is above identical
Conventional graphite energy density on cathode under formulation condition.
The present invention is compound as silicon-carbon using polystyrene-polypropylene acid butyl ester-polystyrene block type copolymer emulsion
The binder of electrode, the mutually non-swelling electrolyte of the styrene at copolymer both ends can be formed together physical crosslinking net with silicon particle
Network maintains electrode structure to stablize, butyl acrylate mutually due to its high resiliency can effective volume change of the offset silicon in removal lithium embedded,
Appropriate swelling electrolyte simultaneously, improves the conduction velocity of lithium ion, when improving carbon-silicon composite material as negative electrode of lithium ion battery
Cycle performance.
Particular embodiments described above has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention,
All within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in of the invention
Within protection scope.
Claims (9)
1. a kind of negative electrode of lithium ion battery based on silicon, the negative electrode of lithium ion battery is to be coated in negative electrode slurry on copper foil to make
Standby and obtain, thickness is between 50-300 microns, which is characterized in that the formula of the negative electrode slurry are as follows: graphite 15.0-18.0 weight
Measure part, nano silica fume 1.0-2.0 parts by weight, conductive agent 0.3-2.5 parts by weight, binder 1.0-8.0 parts by weight, thickener 1.0-
1.5 parts by weight, decentralized medium 70.0-80.0 parts by weight；The binder is polystyrene-polypropylene acid butyl ester-polystyrene
Block type copolymer water-based latex.
2. as described in claim 1 based on the negative electrode of lithium ion battery of silicon, it is characterised in that: the partial size of the graphite is
300-500 mesh, fixed carbon content >=99.0%；The average diameter of the nano silica fume is at 50-100 nanometers.
3. as described in claim 1 based on the negative electrode of lithium ion battery of silicon, it is characterised in that: the conductive agent selects Super
P, Super S, acetylene black, carbon nanotube or carbon fiber.
4. as described in claim 1 based on the negative electrode of lithium ion battery of silicon, it is characterised in that: the thickener is carboxymethyl fibre
Tie up plain sodium.
5. as described in claim 1 based on the negative electrode of lithium ion battery of silicon, it is characterised in that: the decentralized medium is deionization
Water.
6. a kind of preparation method of the negative electrode of lithium ion battery described in claim 1 based on silicon, which is characterized in that including walking as follows
It is rapid:
(1) thickener of 1.0-1.5 parts by weight, the conductive agent of 0.3-2.5 parts by weight, 15.0-18.0 weight are added in ball mill
The graphite of amount part and the nano silica fume of 1.0-2.0 parts by weight, ball milling 120-180 minutes；
(2) step 1 resulting material is transferred to vacuum stirring cylinder, in blender be added 1.0-8.0 parts by weight binder and
The decentralized medium of 46.67-53.33 parts by weight stirs at low speed 5-15 minutes, scraper after stirring, then high-speed stirred 45-60 points
Clock；
(3) decentralized medium of 23.33-26.67 parts by weight is added in the material obtained by step 2, stirs at low speed 5-15 minutes,
Scraper after stirring high-speed stirred 45-60 minutes, obtains the lithium ion battery anode slurry；
(4) negative electrode slurry for obtaining step 3 is coated on copper foil, and coating thickness obtains between 50-300 microns based on silicon
Negative electrode of lithium ion battery.
7. the preparation method of the negative electrode of lithium ion battery based on silicon as claimed in claim 6, which is characterized in that the step 2 and 3
It is carried out under 0.3-0.5 bar vacuum degree condition.
8. the preparation method of the negative electrode of lithium ion battery based on silicon as claimed in claim 6, which is characterized in that the step 1
Rotational speed of ball-mill is 150-300 r/min.
9. the preparation method of the negative electrode of lithium ion battery based on silicon as claimed in claim 6, which is characterized in that the step 2 and 3
In, stirring at low speed speed is 30-50 r/min, and high-speed stirred speed is 150-200 r/min.
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| CN106025347B (en) * | 2016-07-27 | 2019-05-28 | 浙江大学 | A kind of high-energy-density density lithium ion battery |
| US10411264B2 (en) * | 2017-02-27 | 2019-09-10 | Global Graphene Group, Inc. | Cathode active material layer for lithium secondary battery and method of manufacturing |
| CN107565091B (en) * | 2017-08-31 | 2019-12-31 | 浙江大学 | Stretchable electrode of lithium ion battery and preparation method thereof |
| CN108011076B (en) * | 2017-11-27 | 2020-08-28 | 欣旺达电子股份有限公司 | Lithium ion battery, battery pole piece and preparation method thereof |
| CN108417818B (en) * | 2018-02-07 | 2021-05-07 | 浙江大学 | Lithium ion battery cathode based on silicon-based material |
| CN108306021B (en) * | 2018-02-07 | 2020-12-29 | 浙江大学 | Silicon-based lithium ion battery cathode |
| CN108470884B (en) * | 2018-03-20 | 2021-07-13 | 浙江大学 | Lithium ion battery electrode prepared from water-based binder |
| CN108832129B (en) * | 2018-06-13 | 2021-12-17 | 闽南师范大学 | Electrode slurry, preparation method thereof and lithium ion battery electrode prepared from electrode slurry |
| CN109037689B (en) * | 2018-07-20 | 2022-04-15 | 亚士创能科技(上海)股份有限公司 | Preparation method of lithium ion silicon-based negative electrode material, battery negative electrode and lithium battery |
| CN109461910B (en) * | 2018-10-19 | 2021-04-06 | 浙江大学 | Lithium battery positive electrode based on graphene-sulfur composite material and preparation method thereof |
| CN109361009A (en) * | 2018-10-19 | 2019-02-19 | 浙江大学 | A kind of sulphur-silicon lithium battery |
| CN110148718B (en) * | 2019-05-10 | 2021-07-13 | 深圳沃伦特科技有限公司 | Silicon-based slurry and preparation method and application thereof |
| CN111430667B (en) * | 2019-12-31 | 2022-06-21 | 蜂巢能源科技有限公司 | Negative electrode slurry, negative electrode plate, power battery and electric automobile |
| CN112382757B (en) * | 2020-08-11 | 2022-03-18 | 万向一二三股份公司 | Negative electrode composite thickening agent, negative electrode plate and preparation method |
| CN112279981B (en) * | 2020-10-20 | 2023-02-03 | 珠海冠宇电池股份有限公司 | Polymer binder containing soft phase region and hard phase region and preparation method and application thereof |
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